Comprehensive SummaryIn this work, we have successfully obtained a series of novel copper(I)–iodide clusters (CuI NCs) based assembly materials by combining supramolecular pseudorotaxane ligands {[Mebpe+]PF6–@CB[6] (CB[6] = cucurbit[6]uril), L’·PF6} and linkers {BPHF@CB[6], [BPHF = C14H20N4(PF6)2], L·PF6}, including discrete cluster CuI 1 and extended cluster organic frameworks MORF 1 and MORF 2. CuI 1 can be described as a dumbbell‐shaped molecule with its body‐centered site and two vertexes respectively occupied by one [Cu5I6]– cluster and two CB[6] held together by two L’·PF6 ligands. The crystal structures of MORF 1 and MORF 2 are 1D anionic chain and four‐fold interpenetrated 3D cationic diamondoid structure, respectively, which all featured intriguing alternating CB[6] and CuI NCs. Furthermore, CuI 1 exhibits outstanding thermochromic and piezochromic luminescence. MORF 1 and MORF 2 also are detected pressure dependent luminescence properties with an enormous blue‐shift of the near‐infrared (NIR) emission band under high pressure compression. These exciting and smart materials possess great potential in the application field of novel temperature and pressure sensors.